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CN112876355B - Method for preparing carboxylic ester compound by breaking carbon-carbon bond through oxidation of secondary alcohol compound - Google Patents

Method for preparing carboxylic ester compound by breaking carbon-carbon bond through oxidation of secondary alcohol compound Download PDF

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CN112876355B
CN112876355B CN201911198773.4A CN201911198773A CN112876355B CN 112876355 B CN112876355 B CN 112876355B CN 201911198773 A CN201911198773 A CN 201911198773A CN 112876355 B CN112876355 B CN 112876355B
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高爽
王连月
骆慧慧
吕迎
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Dalian Institute of Chemical Physics of CAS
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    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
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    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79—Acids; Esters
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    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
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    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
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    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D333/40—Thiophene-2-carboxylic acid
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
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    • Y02P20/584—Recycling of catalysts

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Abstract

本发明公开一种仲醇类化合物氧化断裂碳碳键制备羧酸酯类化合物的方法。该方法将仲醇类化合物、添加剂及氮掺杂的介孔碳负载的单原子催化剂加入到脂肪伯醇溶剂中，放入压力容器中密闭，通入一定压力的氧源气体，氧源气体压力为0.1‑1MPa，反应温度为80‑150℃，反应后产物为羧酸酯类化合物。本发明采用的氮掺杂介孔碳负载的单原子催化剂，催化剂活性高，反应后产物羧酸酯类化合物分离收率最高达99％，该方法适用范围广，且反应条件容易控制，催化剂可循环使用，后处理简单，适于工业化生产。The invention discloses a method for preparing carboxylate compounds by oxidatively cleaving carbon-carbon bonds of secondary alcohol compounds. In the method, secondary alcohol compounds, additives and nitrogen-doped mesoporous carbon-supported single-atom catalysts are added into aliphatic primary alcohol solvent, put into a pressure vessel and sealed, and a certain pressure of oxygen source gas is introduced, and the pressure of the oxygen source gas is is 0.1-1MPa, the reaction temperature is 80-150°C, and the reaction product is a carboxylate compound. The nitrogen-doped mesoporous carbon-supported single-atom catalyst used in the present invention has high catalyst activity, the separation yield of the product carboxylate compound after the reaction is up to 99%, the method has a wide range of application, and the reaction conditions are easy to control, and the catalyst can Recycling, simple post-processing, suitable for industrial production.

Description

Method for preparing carboxylic ester compound by breaking carbon-carbon bond through oxidation of secondary alcohol compound
Technical Field
The invention relates to the technical field of single-atom catalytic oxidation breaking of carbon-carbon bonds, in particular to a method for directly preparing organic carboxylic ester compounds by oxidative breaking of carbon-carbon bonds of secondary alcohol compounds,
background
The organic methyl carboxylate is a very important chemical product and an organic synthesis intermediate, and is widely applied to the fields of food, organic synthesis, paint, spice, cosmetics, medicine, high polymer materials and the like. Thus, esterification reactions are an important class of organic chemical reactions as a general route to the preparation of esters. The secondary alcohol compound is an important organic compound, can be converted to synthesize various organic chemicals, is esterified by oxidative cleavage of carbon-carbon bonds to obtain organic carboxylic ester, and is an effective way for converting and utilizing the secondary alcohol compound.
The traditional synthesis method of organic carboxylic ester is that acid and alcohol are used as raw materials, concentrated sulfuric acid is used as a catalyst, and the organic carboxylic ester is directly synthesized by esterification after long-time heating. Although the concentrated sulfuric acid used as the catalyst has high activity, the method also has more defects: poor selectivity, more side reactions, poor product purity, and severe environmental pollution and equipment corrosion caused by strong acid. The subsequent mild ester synthesis process is usually carried out by first reacting carboxylic acid with highly active acid chloride, or anhydride, and then reacting with alcohol to produce the corresponding ester. These methods, which require oxidation, activation and esterification steps if an ester is first prepared using an aldehyde as a starting material, generally lower the yield of the ester and require a longer reaction time. Subsequently, further efforts have been directed to the direct oxidative esterification of aldehydes to synthesize esters in one step, but such processes often use stoichiometric or excess amounts of oxidizing agents, e.g., manganese dioxide, potassium hydrogen persulfate, peroxides, and although useful, there are significant amounts of toxic and unwanted by-products formed, and aldehydes as substrates are often oxidized from alcohols. In another method for preparing carboxylic ester, the direct oxidation esterification of primary alcohol is used to synthesize ester substance in one step, but the catalyst used in the method is mainly noble metal Au and Pd, and part of the catalyst system is cobalt-based catalyst loaded by carbon material.
At present, no report exists on a route for obtaining organic carboxylic ester from a secondary alcohol compound through oxidative cleavage esterification of a carbon-carbon bond, and the method not only provides a way for preparing the organic carboxylic ester, but also provides a way for converting and utilizing the secondary alcohol compound.
Disclosure of Invention
The invention provides a new route for obtaining organic carboxylic ester from secondary alcohol compounds through oxidation, breaking and esterification of carbon-carbon bonds, the reaction condition of the route is mild, the carboxylic ester is prepared with high efficiency and low cost, the substrate application is wide, and the product yield is high.
The technical scheme adopted by the invention is as follows:
a method for preparing carboxylic ester compounds by oxidizing and breaking carbon-carbon bonds of secondary alcohol compounds comprises the following steps: adding a secondary alcohol compound, an additive and a nitrogen-doped mesoporous carbon-supported monoatomic catalyst into an aliphatic primary alcohol solvent, placing the aliphatic primary alcohol solvent into a pressure container, sealing the pressure container, introducing oxygen source gas with certain pressure, wherein the pressure of the oxygen source gas is 0.1-1MPa, the reaction temperature is 80-150 ℃, and the product after the reaction is a carboxylic ester compound.
The secondary alcohol compound is one or more than two of the following compounds:
aromatic secondary alcohols:
Figure BDA0002295339270000021
r1 is one or more of H,2-Me,3-Me,4-Me,2-MeO,3-MeO,4-MeO,4-F,4-Cl,4-Br,4-NO2,4-CF3,4-CN,4-tBu,4-Ph, R1The number is 1-5;
Figure BDA0002295339270000022
one or more of R2 ═ H, Me, Ph, OPh and OPh (4-OCH 3);
heterocyclic secondary alcohols: one or more of 3- (1-hydroxyethyl) pyridine, 2- (1-hydroxyethyl) pyridine, DL-1- (2-furyl) ethanol and 1- (thiophene-2-yl) -1-ethanol;
secondary alcohols of fats:
Figure BDA0002295339270000023
n is 1-6, or one or more than two.
The synthetic route is as follows:
Figure BDA0002295339270000024
R3＝H,C1-C9
the additive is an alkaline inorganic compound and comprises one or more of potassium hydroxide, potassium carbonate, sodium carbonate, cesium carbonate and potassium phosphate.
The preparation method of the nitrogen-doped mesoporous carbon-supported monatomic catalyst comprises the following steps: weighing a certain amount of silica sol, adding the silica sol into water, and stirring at room temperature to obtain a mixed solution A; weighing a certain amount of 1, 10-phenanthroline and cobalt acetate, adding the 1, 10-phenanthroline and cobalt acetate into water, stirring at room temperature to obtain a mixed solution B, slowly dropwise adding the solution A into the mixed solution B, stirring the mixture at room temperature for more than 1 hour, then evaporating water in vacuum, drying the obtained solid in vacuum, roasting the solid in a nitrogen atmosphere at 800-900 ℃ for more than 2 hours, soaking the obtained black powder in HF with the mass concentration of 15-30% for more than 24 hours, finally washing the black powder to be neutral by deionized water, and drying the black powder in an oven at 80-120 ℃ to obtain the target catalyst Co-N-C. Wherein the mass content of Co is 0.5-6wt%, and the mass content of N is 1-5 wt%.
The aliphatic primary alcohol solvent is one or more of C1-C10.
The reaction temperature is 80-150 ℃, and the preferable reaction temperature is 130-150 ℃;
the gas pressure is 0.1-1MPa, and the preferable reaction gas pressure is 0.4 MPa;
the reaction time is 6-30h, and the preferable reaction time is 12-24 h.
The oxygen source is one or two of pure oxygen or air.
The molar ratio of the additive to the alcoholic reactant charge is 0.05-0.2, preferably 0.1.
The molar ratio of the added amount of the catalyst to the fed amount of the alcohol reactant is 0.01-0.05, and preferably 0.05. Compared with the existing preparation method of the organic carboxylic ester compound, the preparation method has the following advantages:
the catalyst is a heterogeneous catalyst and is easy to recycle
Wide substrate range, and is suitable for various secondary alcohol compounds
The selectivity of the product carboxylic ester is high, and the by-product is less.
The nitrogen-doped mesoporous carbon-loaded monatomic catalyst adopted by the invention has high catalyst activity, the highest separation yield of the carboxylic ester compound after reaction reaches 99%, the method has wide application range, the reaction condition is easy to control, the catalyst can be recycled, the post-treatment is simple, and the method is suitable for industrial production.
Detailed Description
In order to further explain the present invention in detail, several specific embodiments are given below, but the present invention is not limited to these embodiments.
The preparation method of the nitrogen-doped mesoporous carbon-supported monatomic catalyst comprises the following steps: weighing 5.0g of silica sol, adding the silica sol into 100ml of water, and stirring at room temperature to obtain a mixed solution A; weighing 0.6g of 1, 10-phenanthroline and cobalt acetate, adding into 50ml of water, stirring at room temperature to obtain a mixed solution B, slowly dropwise adding the solution A into the mixed solution B, stirring the mixture at room temperature for 2 hours, then evaporating water in vacuum, drying the obtained solid in vacuum, roasting at 800 ℃ for 2 hours in a nitrogen atmosphere, soaking the obtained black powder in 20% HF for 24 hours, finally washing with deionized water to be neutral, and drying in an oven at 80 ℃ to obtain the target catalyst Co-N-C. Wherein the mass content of Co is 2.3 wt%, and the mass content of N is 3.2 wt%.
Example 1
Mixing Co-N-C (5 mol% relative to the starting material), 1-phenylethanol (1mmol), K2CO3(20 mol%) 4mL of methanol was sequentially added to a 25mL polytetrafluoroethylene-lined autoclave, which was then closedAnd (3) filling oxygen into the reaction kettle, keeping the pressure to be 0.4MPa, putting the reaction kettle into an oil bath at 130 ℃, stirring and reacting for 12 hours at the rotating speed of 400 ℃, cooling the reaction kettle to room temperature after the reaction is finished, opening the reaction kettle, adding internal standard biphenyl (60mg), detecting a qualitative product by gas chromatography-mass spectrometry, and quantifying the conversion rate of the substrate 1-phenyl ethanol and the yield of the product methyl benzoate by a gas chromatography internal standard method shown in table 1.
Example 2
Adding Co-N-C (5 mol%), 1-phenyl ethanol (1mmol), KOH (20 mol%) and 4mL of methanol into a 25mL pressure kettle with a polytetrafluoroethylene lining in sequence, sealing the reaction kettle, filling oxygen to 0.4MPa, putting the reaction kettle into an oil bath at 130 ℃, stirring and reacting for 12 hours at the rotating speed of 400 ℃, cooling the reaction kettle to room temperature after the reaction is finished, opening the reaction kettle, adding internal standard biphenyl (60mg), detecting a qualitative product by gas chromatography-mass spectrometry, and quantifying the conversion rate of the substrate 1-phenyl ethanol and the yield of the product methyl benzoate by the gas chromatography internal standard method shown in Table 1.
Example 3
Mixing Co-N-C (5 mol%), 1-phenyl ethanol (1mmol), Na2CO3(20 mol%) and 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, a qualitative product is detected by gas chromatography-mass spectrometry, and the conversion rate of the substrate 1-phenyl ethanol and the yield of the product methyl benzoate are quantified by the gas chromatography internal standard method and shown in Table 1.
Example 4
Mixing Co-N-C (5 mol%), 1-phenyl ethanol (1mmol), Cs2CO3(20 mol%) and 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, a qualitative product is detected by gas chromatography-mass spectrometry, and the conversion rate of the substrate 1-phenyl ethanol and the yield of the product methyl benzoate are quantified by the gas chromatography internal standard method and shown in Table 1.
Example 5
Mixing Co-N-C (5 mol%), 1-phenyl ethanol (1mmol), K3PO4(20 mol%) and 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, a qualitative product is detected by gas chromatography-mass spectrometry, and the conversion rate of the substrate 1-phenyl ethanol and the yield of the product methyl benzoate are quantified by the gas chromatography internal standard method and shown in Table 1.
Example 6
Mixing Co-N-C (5 mol%), 1- (2-methylphenyl) -1-ethanol (1mmol), K2CO3(20 mol%) and 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, a gas chromatography-mass spectrometry detection qualitative product is obtained, and the yield of a substrate 1- (2-methylphenyl) -1-ethanol and a product 2-methyl benzoate is quantified by a gas chromatography internal standard method and is shown in Table 1.
Example 7
Mixing Co-N-C (5 mol%), 1- (3-methylphenyl) -1-ethanol (1mmol), K2CO3(20 mol%) and 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, a gas chromatography-mass spectrometry detection qualitative product is obtained, and the yield of a substrate 1- (3-methylphenyl) -1-ethanol and a product 3-methyl benzoate is quantified by a gas chromatography internal standard method and is shown in Table 1.
Example 8
Mixing Co-N-C (5 mol%), 1- (4-methylphenyl) -1-ethanol (1mmol), K2CO3(20 mol%) 4mL of methanol was sequentially added to a 25mL polytetrafluoroethylene-lined autoclave, which was then closed and chargedAnd (3) putting the reaction kettle into an oil bath at the temperature of 130 ℃ under the oxygen pressure of 0.4MPa, stirring at the rotating speed of 400 ℃ for reaction for 12 hours, cooling the reaction kettle to room temperature after the reaction is finished, opening the reaction kettle, adding internal standard biphenyl (60mg), detecting a qualitative product by gas chromatography-mass spectrometry, and quantifying the yield of the substrate 1- (4-methylphenyl) -1-ethanol and the product 4-methyl benzoate by the gas chromatography internal standard method in table 1.
Example 8
Mixing Co-N-C (5 mol%), 1- (2-methoxyphenyl) -1-ethanol (1mmol), K2CO3(20 mol%) and 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, a gas chromatography-mass spectrometry detection qualitative product is obtained, and the yield of a substrate 1- (2-methoxyphenyl) -1-ethanol and a product 2-methoxy methyl benzoate is quantified by the gas chromatography internal standard method and is shown in Table 1.
Example 9
Mixing Co-N-C (5 mol%), 1- (3-methoxyphenyl) -1-ethanol (1mmol), K2CO3(20 mol%) and 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, a gas chromatography-mass spectrometry detection qualitative product is obtained, and the yield of a substrate 1- (3-methoxyphenyl) -1-ethanol and a product 3-methoxy methyl benzoate is quantified by the gas chromatography internal standard method and is shown in Table 1.
Example 10
Mixing Co-N-C (5 mol%), 1- (4-methoxyphenyl) -1-ethanol (1mmol), K2CO3(20 mol%) and 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is put into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, and a gas chromatography-mass spectrometry detection qualitative product is obtained,the yields of substrate 1- (4-methoxyphenyl) -1-ethanol and product methyl 4-methoxybenzoate were quantified by gas chromatography internal standard method as shown in Table 1.
Example 11
Mixing Co-N-C (5 mol%), 1- (4-fluorophenyl) -1-ethanol (1mmol), K2CO3(20 mol%) and 4mL of methanol are sequentially added into a 25mL of pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, a qualitative product is detected by gas chromatography-mass spectrometry, and the yield of a substrate 1- (4-fluorophenyl) -1-ethanol and a product 4-methyl fluorobenzoate is quantified by the gas chromatography internal standard method and shown in Table 1.
Example 12
Mixing Co-N-C (5 mol%), 1- (4-chlorophenyl) -1-ethanol (1mmol), K2CO3(20 mol%) and 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, a qualitative product is detected by gas chromatography-mass spectrometry, and the yield of a substrate 1- (4-chlorphenyl) -1-ethanol and a product 4-methyl chlorobenzoate is quantified by the gas chromatography internal standard method and is shown in Table 1.
Example 13
Mixing Co-N-C (5 mol%), 1- (4-bromophenyl) -1-ethanol (1mmol), K2CO3(20 mol%) and 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, a qualitative product is detected by gas chromatography-mass spectrometry, and the yield of a substrate 1- (4-chlorphenyl) -1-ethanol and a product 4-bromobenzoic acid methyl ester is quantified by the gas chromatography internal standard method and is shown in Table 1.
Example 14
Mixing Co-N-C (5 mol%), 1- (4-nitrophenyl) -1-ethanol (1mmol), K2CO3(20 mol%) and 4mL of methanol are sequentially added into a 25mL of pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, a qualitative product is detected by gas chromatography-mass spectrometry, and the yield of a substrate 1- (4-nitrophenyl) -1-ethanol and a product 4-methyl nitrobenzoate is quantified by the gas chromatography internal standard method and is shown in Table 1.
Example 15
Mixing Co-N-C (5 mol%), 1- (4-trifluoromethylphenyl) -1-ethanol (1mmol), K2CO3(20 mol%) and 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, a qualitative product is detected by gas chromatography-mass spectrometry, and the yield of a substrate 1- (4-trifluoromethylphenyl) -1-ethanol and a product 4-trifluoromethylbenzoic acid methyl ester is quantified by the gas chromatography internal standard method and is shown in Table 1.
Example 16
Mixing Co-N-C (5 mol%), 1- (4-cyanophenyl) -1-ethanol (1mmol), K2CO3(20 mol%) and 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, a gas chromatography-mass spectrometry detection qualitative product is obtained, and the yield of a substrate 1- (4-cyanophenyl) -1-ethanol and a product 4-methyl cyanobenzoate is quantified by a gas chromatography internal standard method and is shown in Table 1.
Example 17
Mixing Co-N-C (5 mol%), 1- (4-biphenyl) ethanol (1mmol), K2CO3(20 mol%) 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is put into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, and after the reaction is finished, the reaction is carried outCooling the reaction kettle to room temperature, opening the reaction kettle, adding biphenyl (60mg) as an internal standard, detecting the qualitative product by gas chromatography-mass spectrometry, and quantifying the yield of the substrate 1- (4-biphenyl) ethanol and the product 4-biphenyl methyl benzoate by the gas chromatography internal standard method shown in table 1.
Example 18
Mixing Co-N-C (5 mol%), 1-phenylpropanol (1mmol), K2CO3(20 mol%) and 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, a qualitative product is detected by gas chromatography-mass spectrometry, and the yield of a substrate 1-phenylpropanol and a product methyl benzoate is quantified by the gas chromatography internal standard method and is shown in Table 1.
Example 19
Mixing Co-N-C (5 mol%), diphenylethanol (1mmol), K2CO3(20 mol%) and 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, a qualitative product is detected by gas chromatography-mass spectrometry, and the yield of a substrate, namely the diphenylethanol, and a product, namely the methyl benzoate, is quantified by a gas chromatography internal standard method and is shown in Table 1.
Example 20
Mixing Co-N-C (5 mol%), 2-phenoxy-1-phenylethanol (1mmol), K2CO3(20 mol%) and 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, a gas chromatography-mass spectrometry detection qualitative product is obtained, and the yield of a substrate 2-phenoxy-1-phenyl ethanol and a product methyl benzoate is quantified by a gas chromatography internal standard method and is shown in Table 1.
Example 21
Mixing Co-N-C (5 mol%)) 2- (4-methoxy) phenoxy-1-phenylethanol (1mmol), K2CO3(20 mol%) and 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, a qualitative product is detected by gas chromatography-mass spectrometry, and the yield of a substrate 2- (4-methoxy) phenoxy-1-phenyl ethanol and a product methyl benzoate is quantified by a gas chromatography internal standard method and shown in Table 1.
Example 22
Mixing Co-N-C (5 mol%), 3- (1-hydroxyethyl) pyridine (1mmol), K2CO3(20 mol%) and 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, the qualitative products are detected by gas chromatography-mass spectrometry, and the yield of the substrate 3- (1-hydroxyethyl) pyridine and the product 3-methyl picolinate is quantified by the gas chromatography internal standard method and is shown in Table 1.
Example 23
Mixing Co-N-C (5 mol%), 2- (1-hydroxyethyl) pyridine (1mmol), K2CO3(20 mol%) and 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, a gas chromatography-mass spectrometry detection qualitative product is obtained, and the yield of a substrate 2- (1-hydroxyethyl) pyridine and a product 2-methyl picolinate is quantified by a gas chromatography internal standard method and is shown in Table 1.
Example 24
Mixing Co-N-C (5 mol%), DL-1- (2-furyl) ethanol (1mmol), K2CO3(20 mol%) 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is put into an oil bath at 130 ℃, and the stirring reaction is carried out at 400 rotating speedAnd (2) after the reaction is finished, cooling the reaction kettle to room temperature, opening the reaction kettle, adding internal standard biphenyl (60mg), detecting a qualitative product by gas chromatography-mass spectrometry, and quantifying the yield of the substrate 2- (1-hydroxyethyl) pyridine and the product 2-methyl furoate by a gas chromatography internal standard method, wherein the yield is shown in table 1.
Example 25
Mixing Co-N-C (5 mol%), 1- (thiophene-2-yl) -1-ethanol (1mmol), K2CO3(20 mol%) and 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, a gas chromatography-mass spectrometry detection qualitative product is obtained, and the yield of a substrate 2- (1-hydroxyethyl) pyridine and a product thiophene-2-methyl carboxylate is quantified by a gas chromatography internal standard method and is shown in Table 1.
Example 25
Mixing Co-N-C (5 mol%), 2-hexanol (1mmol), K2CO3(20 mol%) and 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is put into an oil bath at 150 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, the gas chromatography-mass spectrometry is used for detecting qualitative products, and the yield of the substrate 2-hexanol and the product methyl valerate is quantified by the gas chromatography internal standard method and is shown in Table 1.
Example 26
Mixing Co-N-C (5 mol%), 2-octanol (1mmol), K2CO3(20 mol%) and 4mL of methanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 130 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, the qualitative product is detected by gas chromatography-mass spectrometry, and the yield of the substrate 2-octanol and the product methyl heptanoate is quantified by a gas chromatography internal standard method and is shown in Table 1.
Example 27
Mixing Co-N-C (5 mol%), 1-phenylethaneAlcohol (1mmol), K2CO3(20 mol%) and 4mL of ethanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 150 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, a qualitative product is detected by gas chromatography-mass spectrometry, and the conversion rate of the substrate 1-phenyl ethanol and the yield of the product ethyl benzoate are quantified by the gas chromatography internal standard method and are shown in Table 1.
Example 28
Mixing Co-N-C (5 mol%), 1-phenyl ethanol (1mmol), K2CO3(20 mol%) and 4mL of butanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 150 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, a qualitative product is detected by gas chromatography-mass spectrometry, and the conversion rate of the substrate 1-phenyl ethanol and the yield of the product butyl benzoate are quantified by the gas chromatography internal standard method and shown in Table 1.
Example 29
Mixing Co-N-C (5 mol%), 1-phenyl ethanol (1mmol), K2CO3(20 mol%) and 4mL of octanol are sequentially added into a 25mL pressure kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, oxygen pressure is charged to 0.4MPa, the reaction kettle is placed into an oil bath at 150 ℃, the stirring reaction is carried out for 12 hours at the rotating speed of 400 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, the reaction kettle is opened, internal standard biphenyl (60mg) is added, a qualitative product is detected by gas chromatography-mass spectrometry, and the conversion rate of the substrate 1-phenyl ethanol and the yield of the product octyl benzoate are quantified by the gas chromatography internal standard method and are shown in Table 1.
Figure BDA0002295339270000091
Figure BDA0002295339270000101

Claims (7)

1.仲醇类化合物氧化断裂碳碳键制备羧酸酯类化合物的方法，其特征在于：将仲醇类化合物、添加剂及氮掺杂介孔碳负载的单原子催化剂加入到脂肪伯醇溶剂中，放入压力容器中密闭，通入氧源气体，氧源气体压力为0.1-1MPa，反应温度为80-150 oC，反应后产物为羧酸酯类化合物；1. the method for preparing carboxylate compound by oxidative cleavage of carbon-carbon bond of secondary alcohol compound, it is characterized in that: the single-atom catalyst of secondary alcohol compound, additive and nitrogen-doped mesoporous carbon load is added in the aliphatic primary alcohol solvent , put it into a pressure vessel and seal it, feed the oxygen source gas, the oxygen source gas pressure is 0.1-1MPa , the reaction temperature is 80-150 ℃, and the reaction product is a carboxylate compound; 所述的氮掺杂介孔碳负载的单原子催化剂制备方法为：称取一定量的硅溶胶，加到水中，室温搅拌，得到混合溶液A；称取一定量的1，10-菲啰啉和醋酸钴，加入水中，室温搅拌，得混合溶液B，将A溶液慢慢滴加到混合溶液B中，混合物室温下搅拌1小时以上，然后真空蒸出水，所得固体真空干燥，然后在800-900oC氮气氛围下焙烧2小时以上，所得黑色粉末用质量浓度15-30%HF浸泡24小时以上，最后用去离子水洗至中性，80-120oC烘箱内干燥，即得目标催化剂Co-N-C；其中Co质量含量为0.5-6wt%，N的质量含量为1-5wt%；The preparation method of the nitrogen-doped mesoporous carbon-supported single-atom catalyst is as follows: weigh a certain amount of silica sol, add it to water, stir at room temperature to obtain a mixed solution A; weigh a certain amount of 1,10-phenanthroline and cobalt acetate, add water, and stir at room temperature to obtain mixed solution B, slowly drop solution A into mixed solution B, stir the mixture at room temperature for more than 1 hour, then evaporate the water in vacuo, the obtained solid is vacuum-dried, and then dried at 800- Roasting under 900 o C nitrogen atmosphere for more than 2 hours, the obtained black powder is soaked in HF with a mass concentration of 15-30% for more than 24 hours, and finally washed with deionized water until neutral, and dried in an oven at 80-120 o C to obtain the target catalyst Co. -NC; wherein the mass content of Co is 0.5-6wt%, and the mass content of N is 1-5wt%; 所述的仲醇类化合物为下述中的一种：Described secondary alcohol compound is the following one: 芳香仲醇类：
Figure 793682DEST_PATH_IMAGE001
R1 = H, 2-Me, 3-Me, 4-Me, 2-MeO, 3-MeO, 4-MeO, 4-F, 4-Cl,4-Br，4-NO2, 4-CF3, 4-CN, 4-tBu, 4-Ph中的一种；
Figure 179664DEST_PATH_IMAGE002
，R2 =H, Me,Ph, OPh, OPh(4-OCH3)中的一种；Aromatic Secondary Alcohols:
Figure 793682DEST_PATH_IMAGE001
R 1 = H, 2-Me, 3-Me, 4-Me, 2-MeO, 3-MeO, 4-MeO, 4-F, 4-Cl, 4-Br, 4-NO 2 , 4-CF 3 , one of 4-CN, 4-tBu, 4-Ph;
Figure 179664DEST_PATH_IMAGE002
, one of R 2 =H, Me, Ph, OPh, OPh(4-OCH 3 ); 杂环类仲醇：3-(1-羟乙基)吡啶
Figure 428243DEST_PATH_IMAGE003
，2-(1-羟乙基)吡啶
Figure 89031DEST_PATH_IMAGE004
，DL-1-(2-呋喃基)乙醇
Figure 372245DEST_PATH_IMAGE005
，1-(噻吩-2-基)-1-乙醇
Figure 663549DEST_PATH_IMAGE006
中的一种；Heterocyclic secondary alcohols: 3-(1-hydroxyethyl)pyridine
Figure 428243DEST_PATH_IMAGE003
, 2-(1-hydroxyethyl)pyridine
Figure 89031DEST_PATH_IMAGE004
, DL-1-(2-furyl)ethanol
Figure 372245DEST_PATH_IMAGE005
, 1-(thiophen-2-yl)-1-ethanol
Figure 663549DEST_PATH_IMAGE006
one of the 脂肪仲醇类：
Figure 133845DEST_PATH_IMAGE007
n = 1-6，中的一种；Fatty secondary alcohols:
Figure 133845DEST_PATH_IMAGE007
n = 1-6, one of; 所述的仲醇类化合物氧化断裂碳碳键制备羧酸酯类化合物的合成路线为：The synthetic route of the described secondary alcohol compound oxidation cleavage carbon-carbon bond to prepare carboxylate compound is:
Figure 598324DEST_PATH_IMAGE008
Figure 598324DEST_PATH_IMAGE008
Figure 736045DEST_PATH_IMAGE009
Figure 736045DEST_PATH_IMAGE009
 R4选自：
Figure 932671DEST_PATH_IMAGE010
、
Figure 155842DEST_PATH_IMAGE011
、
Figure 158433DEST_PATH_IMAGE012
、
Figure 147730DEST_PATH_IMAGE013
；R4 is selected from:
Figure 932671DEST_PATH_IMAGE010
,
Figure 155842DEST_PATH_IMAGE011
,
Figure 158433DEST_PATH_IMAGE012
,
Figure 147730DEST_PATH_IMAGE013
; 所述脂肪伯醇溶剂为R3CH2OH，其中R3 CH2OH 为甲醇，乙醇或辛醇中的一种；The aliphatic primary alcohol solvent is R 3 CH 2 OH, wherein R 3 CH 2 OH is one of methanol, ethanol or octanol; 所述的添加剂为碱性无机化合物，选自氢氧化钾、碳酸钾、碳酸钠、碳酸铯、磷酸钾中的一种或几种；Described additive is basic inorganic compound, is selected from one or more in potassium hydroxide, potassium carbonate, sodium carbonate, cesium carbonate, potassium phosphate; 氧源为纯氧气或者空气中的一种或二种。The oxygen source is one or both of pure oxygen or air. 2.根据权利要求1所述的仲醇类化合物氧化断裂碳碳键制备羧酸酯类化合物的方法，其特征在于，2. the method for preparing carboxylate compound by oxidative cleavage of carbon-carbon bond of secondary alcohol compound according to claim 1, is characterized in that, 所述反应时间为6-30h。The reaction time is 6-30h. 3.根据权利要求2所述的仲醇类化合物氧化断裂碳碳键制备羧酸酯类化合物的方法，其特征在于，3. the method for preparing carboxylate compound by oxidative cleavage of carbon-carbon bond of secondary alcohol compound according to claim 2, is characterized in that, 所述反应温度为130-150oC；Described reaction temperature is 130-150 ℃ ; 所述气体压力为0.4MPa；The gas pressure is 0.4MPa; 所述反应时间为12-24h。The reaction time is 12-24h. 4.根据权利要求1所述的仲醇类化合物氧化断裂碳碳键制备羧酸酯类化合物的方法，其特征在于，添加剂的加入量与仲醇类反应物投料的摩尔比为0.05-0.2。4. The method for preparing carboxylate compounds by oxidative cleavage of carbon-carbon bonds of secondary alcohol compounds according to claim 1, characterized in that, the mol ratio of the addition amount of the additive and the charging of the secondary alcohol reactant is 0.05-0.2. 5.根据权利要求4所述的仲醇类化合物氧化断裂碳碳键制备羧酸酯类化合物的方法，其特征在于，添加剂的加入量与仲醇类反应物投料的摩尔比为0.1。5 . The method for preparing carboxylate compounds by oxidative cleavage of carbon-carbon bonds of secondary alcohol compounds according to claim 4 , wherein the mol ratio of the addition of the additive and the charging of the secondary alcohol reactant is 0.1. 6 . 6.根据权利要求1所述的仲醇类化合物氧化断裂碳碳键制备羧酸酯类化合物的方法，其特征在于，催化剂的加入量与仲醇类反应物投料的摩尔比为0.01-0.05。6 . The method for preparing carboxylate compounds by oxidative cleavage of carbon-carbon bonds of secondary alcohol compounds according to claim 1 , characterized in that, the molar ratio of the added amount of the catalyst and the charging of secondary alcohols reactants is 0.01-0.05. 7 . 7.根据权利要求6所述的仲醇类化合物氧化断裂碳碳键制备羧酸酯类化合物的方法，其特征在于，催化剂的加入量与仲醇类反应物投料的摩尔比为0.05。7. The method for preparing carboxylate compounds by oxidative cleavage of carbon-carbon bonds of secondary alcohol compounds according to claim 6, characterized in that, the mol ratio of the addition of the catalyst to the charging of the secondary alcohol reactants is 0.05.
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